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The spin-state equilibria of cobalt ions in the system La1−xNaxCo1−xNbxO3 (x⩽0·40) has been studied by measuring its magnetic susceptibility as a function of temperature in the range 300–600 K. It is found that the behaviour of the samples withx⩽0·10 is similar to that of LaCoO3, while compositions withx⩾0·20 behave quite differently, exhibiting simple paramagnetic behaviour.